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Alkali Metal Cation Affinities of Anionic Main Group‐Element Hydrides Across the Periodic Table
Author(s) -
Boughlala Zakaria,
Fonseca Guerra Célia,
Bickelhaupt F. Matthias
Publication year - 2017
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201700956
Subject(s) - affinities , alkali metal , chemistry , rubidium , periodic table , density functional theory , main group element , lithium (medication) , caesium , group (periodic table) , computational chemistry , proton , proton affinity , inorganic chemistry , potassium , stereochemistry , transition metal , organic chemistry , ion , protonation , nuclear physics , medicine , physics , endocrinology , catalysis
We have carried out an extensive exploration of gas‐phase alkali metal cation affinities (AMCA) of archetypal anionic bases across the periodic system using relativistic density functional theory at ZORA‐BP86/QZ4P//ZORA‐BP86/TZ2P. AMCA values of all bases were computed for the lithium, sodium, potassium, rubidium and cesium cations and compared with the corresponding proton affinities (PA). One purpose of this work is to provide an intrinsically consistent set of values of the 298 K AMCAs of all anionic (XH n ‐1 − ) constituted by main group‐element hydrides of groups 14–17 along the periods 2–6. In particular, we wish to establish the trend in affinity for a cation as the latter varies from proton to, and along, the alkali cations. Our main purpose is to understand these trends in terms of the underlying bonding mechanism using Kohn–Sham molecular orbital theory together with a quantitative bond energy decomposition analyses (EDA).